KR910002084B1 - Moisture-curable polyurethane compositions - Google Patents

Abstract

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Description

Water Curable Polyurethane Compositions and Manufacturing Method Thereof

The present invention relates to a moisture curable polyurethane composition. The present invention also relates to moisture curable polyurethane adhesives, coatings, sealers and casting materials.

U.S. Patent Nos. 3,707,521, 3,779,794 and 4,511,626 describe some moisture curable polyurethane compositions used to bond automotive windshields and backlights to vehicle bodies. These compositions typically require the use of free primers. When the primers are excluded, insufficient bond strength occurs. As long as suitable bond strength is maintained, it is desirable to eliminate the need for primers, because the individual packaging and application of the primers is cumbersome and increases the cost.

U. S. Patent No. 3,723, 163 describes a moisture curable polyurethane composition for use in connecting concrete. This composition is typically used with primers. If the primer is missing, the composition loses adhesion to the concrete substrate after several days of exposure to moisture or humidity. It is preferable not to use the primer if the proper binding force is maintained. As with the windshield sealant described above, the individual packaging and application of the concrete seal primer involves extra cost and hassle.

US Pat. No. 4,502,479 describes orthopedic casts made from fiber webs impregnated with some moisture-curable polyurethane compositions. Although the cast is light weight, it is desirable to reduce the weight even more.

The present invention is directed to isocyanate-functional polymers and silanes, characterized in that the adhesion of the composition to substrates such as unprimed metals, glass and concrete is enhanced by adding the effective amount of terpene-phenolic resin to the composition. It is provided in some improved water-curable polyurethane compositions that contain a nearly homogeneous mixture of compounds. The surprising improvement in adhesion is especially noticeable after the curing composition has been exposed to moisture, high humidity or ultraviolet radiation. When filled with filler, the composition saves cost without undue loss of adhesion. When glass bubbles are used as fillers, the composition has a reduced density and sag.

In the practice of the present invention, the moisture-curable composition can be reacted with moisture in the atmosphere or with added moisture to produce polymeric polyurethane compositions useful for adhesives, coatings, sealants or cast resins and the like. The composition of the present invention contains isocyanate-functional prepolymers, terpene-phenolic resins and silane compounds.

Isocyanate-functional prepolymers (hereinafter, abbreviated as “prepolymers”) comprise sufficient isocyanate groups that can be cured or polymerized when the composition is exposed to air or added moisture. Suitable prepolymers are described in the "urethane polymers", Kirk-Othmer Encyclopedia of Chemical Technolygy, 3rd Edition, 23, 576-608 (1983) as well as in the above patents and their cited documents. Other suitable prepolymers are those known to those skilled in the art of making water-curable urethane compositions.

These prepolymers are prepared using conventional methods. Typically prepared by reacting an excess of one or more polyisocyanates with one or more polyols to produce a nearly linear prepolymer having residual isocyanate functionality.

It is preferred that the silane compound does not have enough active hydrogen-containing functional groups to cause premature gelation of the prepolymer. If such groups are present, they can be reacted with a suitable active hydrogen-reactive group before the silane compound and the prepolymer bond. Preferably, the silane compound is at least one alkoxy group (eg methoxy or ethoxy group), most preferred is methoxy group. Suitable silane compounds include mercaptosilanes, primary and secondary aminosilanes, epoxy silanes and acrylic silanes. Mercaptosilanes and secondary aminosilanes are preferred.

Particularly preferred silane compounds are isocyanate-reactive silanes (e.g. mercaptosilanes) and excess (e.g. 3: 1 or more based on available reactors) polyisocyanates (e.g. toluene diisocyanate, hexamethylene diisocyanate, hexamethylene di Addition reaction product prepared by reacting a biuret of isocyanate, isophorone diisocyanate or 4,4'-diphenylmethane diisocyanate) to form an isocyanate-functional silane compound. Suitable silane compounds are also described in US Pat. Nos. 3,560,543, 3,627,722, 3,707,521, 3,779,794, 3,808,018 and 3,955,036. Suitable silane compounds on the market include "A-151" vinyltriethoxysilane, "A-153" phenyltriethoxysilane, "A-162 methyltriethoxysilane," A-174 "acrylatotris methoxysilane , "A-186" 3, 4-epoxycyclohexylmethyltrimethoxysilane, "A-187" glycidoxypropyl trimethoxysilane, "A-189" gamma-mercaptopropyltrimethoxysilane, "A -1100 "gamma-aminopropyltriethoxysilane and" A-1120 "N- (trimethoxysilylpropyl) ethylenediamine (all of which are commercially available from Union Carbide Corporation) and" Z-6070 "methyltrimethoxysilane , "z-6071" phenyltrimethoxysilane, "Z-6072" dimethyl dimethoxysilane, "Z-6073" methylphenyldimethoxysilane, "Z-6074" diphenyldimethoxysilane, "Z-6020" N- (Trimethoxysilylpropyl) ethylenediamine, "XZ-2-2023" N- (dimethoxymethylsilylisobutyl) ethylenediamine, "Z-6030" gamma-methacryloxypropyltrimethoxysilane, "Z-6040 Gamma-Glish Oxy propyl trimethoxysilane, and "XZ-8-0999" gamma-chloropropyl trimethoxy silane include (all of which are commercially available from Dow Corning Corporation).

Silane compounds are typically obtained as a clear liquid. They can be added with the prepolymer itself or with a suitable solvent. Suitable solvents include non-reactive organics such as toluene, naphtha, methylethylketone and the like.

The amount of silane compound is preferably adjusted to provide the necessary handling properties before curing and the required level of adhesion after curing (measured initially and after exposure to environmental conditions). The above amounts (hereinafter referred to as "effective amounts") will vary depending on the particular prepolymer conditions and substrates used and the like.

In general, an effective amount of a silane compound is an amount that lacks the adhesion of the composition when the composition is applied between two substrates and aged under environmental conditions, and then subjected to an adhesion test (eg, a peel test). Numerically, the preferred amount of silane compound is 0.1 to 25 parts by weight of the silane compound per 100 parts prepolymer, and more preferably about 1 to 10 parts by weight per 100 parts prepolymer.

Terpene-phenolic resins are polymerization addition products prepared by reacting one or more substituted or unsubstituted phenols with one or more terpenoids. The resulting addition product is preferably sufficiently free of unreacted hydroxyl groups or other active hydrogen-containing functional groups, so that pregelatinization of the polymer does not occur when bound to the prepolymer.

The likelihood of gelling can be reduced by reacting the terpene-phenolic resin with a suitable active hydrogen-reactive species (eg isocyanate or polyisocyanate) prior to bonding the resin with the prepolymer. Preferably, the terpene-phenolic resin has about 200 or less hydroxyl groups. In addition, the resin is preferably alkylated. In addition, the ratio of terpene to phenol is preferably at least about 1.0: 1, even more preferably at least about 2.5: 1 and a lower ratio tends to delay the curing rate of the composition of the present invention. Various terpene-phenolic resins are commercially available, such as "PICCOFYN" series "A100", "A115", "T125" and "A135" resins (available from Hercules, Incorporated), "PICCOFYN" series "MO267" and "MO293" Commercially available from Hercules, Incorporated), "SP-553", "SP-559" and "Sp-560" resins (available from Schenectady Chemicals, Inc.), "NIREZ" based "2019", "V-2040" , "2092" and "V-2150" and "Super Beckacite" based "2000" resins (available from Reichold Chemicals, Inc.) and "Croturez" based "AP-120" resins (available from Crosby Chemicals, Inc.). Included.

Terpene-phenolic resins are typically in the form of yellow or brown flake or lump solids. In order to combine these with a prepolymer, it is usually convenient to dissolve the resin in a solvent or a plasticizer. Suitable solvents include toluene, xylene, acetone, ethyl acetate, "cellulose acetate" (commercially available from Union Crbide Corporation), methylethylketone and the like. Suitable plasticizers include "HB-40" partially hydrogenated terphenyl and "Santicizer 160" butyl benzyl phthalate (these are commercially available from Monsanto Corp.), dioctylphthalate, dibutyl phthalate, diisomesyl phthalate, tricresyl phosphate, and the like. There is this.

Terpene-phenolic resins are preferably adjusted to provide the necessary handling properties before curing and the degree of adhesion required after curing (initial and measured after exposure to environmental conditions such as heat, light, moisture). This amount (hereinafter referred to as "effective amount") depends on the particular prepolymer used, the other ingredients and substrates present in the composition, and the environmental conditions in which the composition is to be used.

Generally, an effective amount of terpene-phenolic resin is applied to a desired substrate and aged under environmental conditions. Amount that indicates lack of adhesion of the composition when subjected to an adhesion test (e.g. film test). In numerical terms, the preferred amount of terpene-penic resin is about 0.1 to 100 parts by weight and even more preferably about 10 to 50 parts by weight per 100 parts of prepolymer.

The compositions of the present invention may contain other adjuvants to provide the necessary handling properties and curability. Suitable auxiliaries include catalysts, reinforcing fillers, expansion fillers, solvents, plasticizers, desiccants, inhibitors, thixotropic agents, UV absorbers, UV stabilizers, antioxidants, thickeners, pigments, surfactants, humectants and dispersants and the like. Other cured or uncured polymers may be added to the composition as needed. The amount and type of adjuvant will vary depending on the particular prepolymer used, the other ingredients and substrates present in the composition, and the environmental conditions in which the composition is to be used. Such adjuvants are typically chosen and their amounts are adjusted based on empirical techniques and tests well known to those skilled in the art. Suitable catalysts include organometallic compounds such as dibutyltindilaurate, dibutyltin diacetate, steners octoate, and the like, triethylenediamine, dimethylpyreazine, zinc oxide or titanium dioxide, minerals (e.g. talc, clay, silica, etc.). ) And organic bubbles. Organic bubbles, as known from US Pat. No. 3,365,315, are particularly preferred fillers because they can reduce the density and cost of the composition. Suitable solvents and plasticizers include those described above. Toluene is the preferred solvent. Partially hydrogenated terphenyl is a preferred plasticizer. Suitable desiccants include molecular sieves such as sodium aluminum silicate and desiccants such as zeolites, silica gel, barium oxide and calcium oxide.

The compositions of the present invention can be packaged and stored according to techniques known to those skilled in the art. Suitable packaging includes, for example, culled tubes (eg made of paper, metal or plastic), compressible tubes equipped with threaded stoppers, cans, drums and the like.

The composition of the present invention is cured by exposure to water, ie water vapor or moisture. Usually, the ambient humidity is suitable for promoting hardening. Heat or high humidity accelerates curing and low temperatures (eg below 5 ° C) or low humidity (eg 15% relative humidity) delays curing. Bonds to wet substrates (eg wood) generally cure faster than bonds to dry substrates (eg glass).

The compositions of the present invention can be used in any application where high-performance adhesives, coatings, sealants or cast resins and the like are required. The use includes the combination of raw glass or alternative glass (eg backlights of laminated shield and safety glass) to vehicles such as automobiles, trucks, airplanes, trains and the like. When used therein, the compositions of the present invention provide fast travel time after glass installation. Other building constructions (e.g. structural adhesives, panel adhesives, humidity barriers, or glazing sutures), assembly line fabrication (e.g. partial assembly of windows by means of adhesive bonding), laminates (e.g. skis) Lamination), coatings (e.g., concrete delay coatings or roofing membranes), seals (e.g. seawater seals or cable splice housings) and casts of moisture curable orthopedic surgeons. The compositions of the present invention can be applied to various shaped articles and substrates such as glass, metal, plastic, wood, leather, masonry, textiles and the like.

The following examples are provided to aid the understanding of the present invention and are not intended to limit the scope of the invention. Unless otherwise indicated, all parts are parts by weight.

Filled Prepolymer A

315 parts of 4,4'-diphenylmethine diisocyanate and 400 parts of "LHT 28" polyol (6,000 MW triol with secondary hydroxyl group, commercially available from Union Carbide Corporation) are sealed reaction vessels equipped with a stirrer and a nitrogen atmosphere. Mixing in to make an isocyanate-functional prepolymer. The mixture is heated to 60 ° C. to dissolve the disiscyanate. Next, 1000 parts of "Polymeg 2000" polyol (2,000 MW diol with primary hydroxyl group, commercially available from Quaker Oats Co.) was heated to 60 ° C. and added to the reaction vessel, followed by 180 parts of “HB-40” plasticizer ( Partially hydrogenated terphenyl, commercially available from Monsanto Corp.). After all the components have been added, the reaction mixture is maintained at 60 ° C. for 4 hours with stirring under nitrogen. The resulting prepolymer is cooled to 40 ° C. and stored in a containment vessel under nitrogen and denoted as “Prepolymer 1”. 150 parts of "Cab-O-SilM5" fumed silica (commercially available from Cabot Corp.), 50 parts of zinc oxide, 500 parts of talc, 76.5 parts of titanium dioxide, 60 parts of 95: 5 to 1500 parts of prepolymer 1; Isooctyl Acrylate Solution Copolymer Thickener, 200 parts "HB-40" plasticizer, 155 parts toluol, 3 parts "Niax A-99" catalyst (bis [2-N, N-dimethylaminoethyl] ether, Union Commercially available from Carbide Corporation), 0.4 part dibutyline dilaurate, 6.1 parts brown iron oxide pigment and 12.3 parts brown iron oxide pigment are added. These components are stirred under nitrogen to obtain a homogeneous mixture. This mixture is stored in a sealed container under nitrogen and denoted as "filled prepolymer A".

Filled Prepolymer B

200 parts of "Regal 300R" furnace carbon black (commercially available from Cabot Corp.) and 75 parts of "Mesamoll" plasticizer (alkyl sulfonic acid ester of phenol, commercially available from Mobay Chemical Corp.) and 1.5 parts of 535 parts of prepolymer 1 Add the "Niax A-99" catalyst. These components are stirred under nitrogen to obtain a homogeneous mixture. The resulting mixture is stored in a sealed container under nitrogen and denoted as "filled prepolymer B".

Filled Prepolymer C

312 parts of 4,4'-diphenylmethane diisocyanate and 400 parts of "LHT28" polyol are combined in a reaction vessel equipped with a stirrer and an atmosphere. The mixture is heated to 60 ° C. to dissolve the diisocyanate. Next, a mixture of 500 parts of "Polymeg 2000" polyol and 750 parts of "PPG 3025" polyol (3000 M.W.diol with secondary hydroxyl group, commercially available from Union Carbide Corporation) was heated to 600 ° C. and added to the reaction vessel. 180 parts of "HB-40" are added.

After all the components have been added the reaction mixture is maintained at 60 ° C. for 4 hours with stirring under nitrogen. The resulting prepolymer is cooled to 40 ° C. and stored in a containment vessel under nitrogen and denoted as “Prepolymer 2”. 75 parts of "Cab-O-Sil M5" fumed silica in 750 parts of prepolymer 2 25 parts of zinc oxide, 250 parts of talc, 40 parts of "Raven 410" furnace carbon black (commercially available from Cities Service Co.), 30 parts of coal tar, 100 parts "HB-40" plasticizer 150 parts varnish maker and painter naphtha, 1.5 parts "Niax A-99" catalyst and 0.19 parts dibutyltin dilaurate are added.

These components are stirred under nitrogen to obtain the admixture. This mixture is stored in a sealed container under nitrogen and denoted as "filled prepolymer C".

Filled Prepolymer D

In a reaction vessel equipped with a stirrer and a nitrogen atmosphere, 348 parts of toluene diisocyanate, 1500 parts of "PPG 3025" polyol and 2000 parts of "LHT28" polyol are combined. The mixture is heated to 80 ° C. and held at that temperature for 4 hours and then cooled to 40 ° C. Next, 4 parts of dibutyltin dalaurate are added and the mixture is stirred for 4 hours.

These components are stirred under nitrogen to obtain a homogeneous mixture. The mixture is stored in a sealed container under nitrogen and labeled "Prepolymer 3".

To 1000 parts of prepolymer 3, add 48 parts of "Cab-O-Sil M5" fumed silica, zinc oxide and titanium dioxide, 662 parts of talc, 25 parts of acrylic solution copolymer thickener, 3.7 parts of brown iron oxide pigment, 7.6 parts of sulfur Brown iron oxide pigment and 0.24 parts of dibutyltin dilaurate are added.

These components are stirred under nitrogen to obtain a homogeneous mixture. The resulting mixture is stored in a sealed container under nitrogen and denoted as "filled prepolymer D".

Filled Prepolymer E

500 parts of talc in 1015 parts of prepolymer 3, 120 parts of "Cab-O-Sil EH5" fumed silica (available from Cabot Corp.), 50 parts of titanium dioxide and zinc oxide, 138 parts of varnish maker and painter naphtha, 130 parts Mineral oil, 60 parts of acrylic solution copolymer thickener and 5 parts of dibutyltin dilaurate are added.

These components are stirred under nitrogen to obtain a homogeneous mixture. The resulting mixture is stored in a sealed container under nitrogen and labeled "filled prepolymer E".

Filled Prepolymer F

A sample of "urethane E" some moisture curable polyurethane windshield suture (commercially available from Essex Chemical Corp.) is taken out of its original packaging and placed in a sealed container under nitrogen and labeled "filled Epolymer F".

Filled Prepolymer G

Samples of "EC-5893" moisture curable polyurethane concrete ground coating (commercially available at 3M) are designated as "filled prepolymer G".

Filled Prepolymer H

To 535 parts of prepolymer 1 is added a solution of 200 parts of "Regal 300R" furnace carbon black and 1.5 parts of "Niax A-99" catalyst in 25 parts of "Mesamoll" plasticizer. These components are stirred under nitrogen to obtain a homogeneous mixture. The resulting mixture is stored in a sealed container under nitrogen and denoted as "filled prepolymer H".

Example 1

A 0.5-0.76 mm thick dispersion of filled prepolymer A is brushed on a solvent free pane and covered with a 25 mm wide canvas and cured at 25 ° C. and 50% relative humidity for 7 days. The cured granules are immersed again in tap water for 25 days.

Immediately after the water is removed, the canvas strip can be pushed out of the glass by lightly pulling a finger, a lack of adhesion occurs at the contact area of the glass-adhesive. When measured with an "Instron" tension tester operated at a crosshead separation rate of 51 mm / min, the observed peel strength was <0.2 kg / cm wide.

The second adhesive composition is prepared as follows. In a reaction vessel equipped with a stirrer, reflux condenser and nitrogen atmosphere, 1610 parts of "Desmodar N-75" hexamethylene diisocyanate biuret (commercially available from Mobay Chemical Co.), 427 parts of "A-189" gamma-mercapto Combine propyl triethoxy silane with 1.3 parts dimethylpiperazine. The mixture is stirred at 80 ° C. for 2 hours and then cooled to room temperature.

6 parts of the silane compound obtained are mixed with 271.3 parts of filled prepolymer A. The adhesion of the obtained composition to unprimed glass is measured as described above. Immediately after removal from water, a hand pull is usually required to remove the canvas strip from the glass and a lack of adhesion pattern is observed. The measured peel strength was 3.0 kg / cm wide.

Both compositions do not contain terpene-phenolic resins. In order to measure this effect, a third adhesive composition is prepared as follows. 69.9 parts of “Super Beckacite 2000” Tefpene-phenolic resin (commercially available from Reichold Chemicals, Inc.) is dissolved in 30 parts of toluol and 6 parts of the above silane compound and 271.3 parts of filled prepolymer A are mixed. The glass adhesion of the obtained composition is measured as described above. Immediately after removal from water, removing the canvas strip from the glass requires a very strong hand pull and lack of adhesion is observed. The measured peel strength was 4.5 kg / cm wide. This example illustrates the improved performance of the composition of the present invention. A strong, water resistant bond to nonprimary glass is obtained. The sesame seed composition (containing terpene-phenolic resin and silane compound) binds the glass with sufficient strength. This is a requirement for automobile manufacturing without the use of glass primers. If terpene-phenolic resins or silane compounds are excluded, the use of separate free primers will be necessary.

Example 2

The third composition of Example 1 is applied to several substrates, covered with a canvas strip, cured, immersed in water and evaluated as described above. For comparison, terpene-phenolic resins are excluded or replaced with planar terpene resins ("PICCOLYTE A-135", available from Hercules, Incorporated). Table 1 shows the substrates and measured peel strengths of each composition.

TABLE 1

(1) chilled steel

(2) galvanized steel

(3) polystyrene, ethanol-wiped

(4) Polymethyl methacrylate, ethanol-wiped.

This example shows that the inclusion of terpene-phenolic resins improves adhesion to various substrates. Substitution of planar terpene resins did not provide a comparable improvement.

Example 3

75 parts of "PICCOFYN A-135" terpene-phenolic resin are dissolved in 25 parts of toluene. The mixture is mixed in various amounts into four separate mixtures, each of which contains 2.2 parts of the silane compound of Example 1 and 97.8 parts of filled prepolymer A. The resulting composition contains 5.0, 12.6, 25.2 and 50.5 parts terpene-phenolic resins per 100 parts filled prepolymer, respectively. The film adhesion to these compositions is measured as in Example 2. Table 2 shows the substrates and the peel strengths measured for each substrate. For comparison, the values of the "no resin" column of the table are listed in Table 2. In the table, a hi-phone (---) indicates that no data was obtained at all. Tensile strength and elongation values for each of the four terpene-phenolic resin-containing compositions are also shown.

TABLE 2

This example illustrates the use of various terpene-phenolic resins. Improvements in adhesion have been observed on various substrates.

Example 4

In a series of four runs, one of two different silane compounds and a terpene-phenolic resin is added to the filled prepolymer B. In some implementations, additional carbon black or plasticizers are used to control handling and curability. Using the method of Example 1, the obtained composition is used in nonprimary glass, coated with canvas, cured and then immersed in water.

In addition, 6 mm foam of each composition is applied to the nonprimary glass and the glass is lateral to the Atlas brand “Weather-O-Meter” for 7 days and then peeled from the glass to measure the UV resistance of each composition.

Table 3 below shows the amount of each component and the binding deficiency pattern measured for each composition.

TABLE 3

(1) "PICCOFYN A-135" terpene-phenolic resins

(2) "A-189 gamma-mercaptopropyltrimethoxy silane

(3) The silane compound of Example (1)

(4) "Regal 300R" furnace carbon black. The amounts shown are other than the existing amounts of prepolymer B filled.

(5) "Mesamoll" plasticizers, the amounts given are other than the existing amounts of filled prepolymer B.

The tack-free time of the composition was 5, 8, 7 and 7 minutes for Examples 1-4, respectively. This example is used to obtain a terpene-phenolic resin to obtain a composition that is resistant to moisture and UV exposure when applied to nonprimary glass, as evidenced by the preferred adhesion deficiency aspect of the composition in water and UV exposure tests. And the presence of a silane compound.

Example 5

In a series of two runs, terpene-phenolic resins and silane compounds are applied to the filled prepolymer C. In a first run, 35 parts of the silane compound of Example 1 were applied to 1451.7 parts filled prepolymer C. In a second run, 375 parts of "PICCOFYN A-135" terpene-phenolic resin was dissolved in 161 parts of toluol and added to 1451.7 parts of 35 parts of the silane compound of Example 1 and the prepolymer C filled. Using the method of Example 1, the resulting composition is evaluated for adhesion to various substrates. Table 4 below shows the substrate and the observed peel strength for each run.

TABLE 4

(1) Acrylonitrile-butadiene-styrene, ethanol-wiped.

(2) Ethanol-wiped.

This example shows that the compositions of the present invention provide significantly increased adhesion to various nonprimary substrates. The results for glass, aluminum, polycarbonate, ABS and fiberglass are particularly beneficial.

Example 6

In four series of runs, terpene-phenolic resins and silane compounds are added to the filled prepolymer D. Using the method of Example 1, the resulting composition is tested for adhesion to various substrates. Table 5 below shows the measured adhesion to the components of the composition and the temporary substrate.

TABLE 5

(1) "PICCOFYN A135" terpene-phenolic resin

(2) Silane Compound of Example 1

This example shows that the composition of the present invention provides a particularly beneficial increase in adhesion to nonprimary glass, aluminum and galvanized steel.

Example 7

In three series of runs, planar terpene resins, terpene-phenolic resins and silane compounds are added to the filled prepolymer D. Using the method of Example 1, the test compositions are measured for adhesion to various substrates of the resulting composition. Table 6 shows the components of each composition and the measured adhesion to each substrate.

TABLE 6

(1) "PICCOLYTE C-115" terpene resin (commercially available from Hercules, Incorporated)

(2) "PICCOFYN A-135" terpene-phenolic resins

(3) The silane compound of Example 1.

This example shows that the compositions of the present invention provide improved adhesion to glass and metal substrates, but not compositions containing planar terpene resins and compositions lacking silane compounds.

Example 8

In four series of runs, terpene-phenolic resins and silane compounds are added to the filled prepolymer F. Using the method of Example 1, the adhesion of the resulting compositions to various substrates is measured. Table 7 below shows the components of the gal composition and the measured adhesion to each substrate.

TABLE 7

(1) "PICCOFYN A-135" terpene-phenolic resins

(2) The silane compound of Example 1.

This example shows that the composition of Example 1 (typically a commercially available encapsulant) can have improved adhesion to all substrates. The composition of the present invention (Ex. 4) provides the most improved adhesion to the steel substrate. For glass, the film adhesion of the composition of Example No. 3 outperforms the value obtained with the composition of the present invention. However, after UV exposure, measurement of adhesion demonstrates that the compositions of the present invention provide better adhesion to glass than the compositions of Run Nos. 1-3.

Example 9

In the four types of drilling, terpene-phenolic resin and silane compound are added to the filled prepolymer G. The resulting composition is applied to a clean, unprimed concrete slab as a 3 mm thick film, covered with a canvas strip and cured at 25 ° C. and 50% R.H for 3 days. The coated cocrete sample was immersed in tap water at 25 ° C. and then measured for several hours on the adhesion of the coating to the concrete. The qualitative test of the adhesion is carried out after each sample is removed from water. The forces and binding deficiencies required to remove the coating by hand were recorded. If the composition lacked adhesion, the next test was stopped.

TABLE 8

(1) "PICCOFYN A-135" terpene-phenolic resins

(2) Silane Compound of Example 1

(3) weak = easily removed

Normal-removed with a slight pull

Strong = Removed only by continuing to pull

This example shows that the composition of Example 1 (usually a commercially available surface coating) provides improved adhesion to unprimed cocreates.

Example 10

In two series of runs, terpene-phenolic resins, silane compounds and glass bubbles are added to the filled prepolymer H. In the first run, 112 parts of "PICCOFYN A-135" terpene-phenolic resin, 66 parts of "Mesamoll" plasticizer and 22 parts of toluene were mixed together and 761.5 parts of filled prepolymer H, 10 parts of "Cab-O-Sil M5" The fumed silica was mixed with 35 parts of the silane compound of Example 1. The resulting composition has very suitable flowability for use in manual caulking rifle equipment.

In the second implementation, fumed silica is replaced with 75 parts of "C15 / 250" glass bubbles (commercially available at 3M). The resulting composition has a fluidity that is very suitable for use in air operated equipment.

Claims (6)

Water-curable, which contains a nearly homogeneous mixture of isocyanate-functional prepolymers and silane compounds, and an effective amount of terpene-phenolic resin is added to improve adhesion to substrates such as non-primary metals, glass and concrete Polyurethane composition. The composition according to claim 1, wherein the terpene-phenolic resin has a hydroxyl group of 200 or less. The composition of claim 1, wherein the terpene-phenolic resin has a ratio of terpene: phenol of at least 1.0: 1. The composition of claim 1 containing from 0.1 to 100 parts by weight of said resin per 100 parts of said prepolymer. The composition of claim 4 containing from 10 to 50 parts by weight of resin per 100 parts of said prepolymer. Coating a primary substrate, characterized by applying a moisture-curable polyurethane layer containing the composition of claim 1 to the primary substrate, optionally applying the secondary substrate to the layer and allowing the composition to cure. How to combine secondary substrates.